Anthraquinone compounds

ABSTRACT

New anthraquinone compounds of the formulae   AND   IN WHICH X1 denotes a hydroxyl or amino group, X2 denotes a hydroxyl, amino, alkylamino, cycloalkylamino, arylamino, acylamino, alkylmercapto or arylmercapto group, Y represents hydrogen, halogen, alkylmercapto or arylmercapto radicals, R represents an alkyl radical, Hal represents chlorine, bromine or iodine and Z represents hydrogen or an acyl radical, AS WELL AS THEIR MANUFACTURE AND USE FOR DYEING AND PRINTING SYNTHETIC FIBRE MATERIALS.

Hederieh et a1.

[451 titt arms ANTI-IRAQUINONE COMPOUNDS [75] Inventors: VollcerHederich, Cologne; Dieter Dieterieli, Leverkusen; Helmut Reiti; GiinterGehriie, both of Cologne, all of Germany [73] Assignee: EayerAlrtiengeselllschatt,

Leverkusen-Bayerwerk, Germany [22] lFiled: Sept. 29, 1972 [21] Appl.No.: 293,590

[30] Foreign Application Priority Data Sept. 30, 1971 Germany 2148849[56] References Cited UNITED STATES PATENTS 2,844,598 7/1958 Gunthard260/380 3,572,986 3/1971 Gehrke 260/380 3,642,835 2/1972 Hederich et al.260/380 3,687,985 8/1972 Maier 260/376 3,694,467 9/1972 Maier 1 260/3803,740,186 6/1973 Hederich et a1. 260/377 FOREIGN PATENTS OR APPLICATIONS973,336 10/1964 United Kingdom 260/380 Primary ExaminerLorraine A.Weinberger Assistant Examiner--E. Jane Skelly Attorney, Agent, orFirmPlumley & Tyner [57] AlES'lIRACT New anthraquinone compounds of theformulae and in which X denotes a hydroxyl or amino group,

X denotes a hydroxyl, amino, alkylamino, cycloalkylamino, arylamino,acylamino, alkylmercapto or arylmercapto group,

Y represents hydrogen, halogen, alkylmercapto or arylmercapto radicals,

R represents an alkyl radical,

l-Ial represents chlorine, bromine or iodine and Z represents hydrogenor an acyl radical,

as well as their manufacture and use for dyeing and printing syntheticfibre materials.

Claims, No Drawings ANTHRAQUINONE CUB [POUNDS The subject of the presentinvention are new anthraquinone compounds of the formula in which Xdenotes a hydroxyl or amino group,

X denotes a hydroxyl, amino, alkylamino, cycloalkylamino, arylamino,acylamino, alkylmercapto or arylmercapto group,

R denotes an alkyl radical and Y denotes hydrogen, halogen or analkylmercapto or arylmercapto radical,

as well as their manufacture and use.

Suitable allcylamino radicals X are those with 1-6 C atoms.

Suitable cycloalkylamino groups X are especially cyclohexylaminoradicals which are optionally substituted by C C -alkyl radicals.

Suitable arylamino radicals X are preferably phenylamino radicals whichcan be substituted by halogen atoms, C -C -alkyl, (h-Q-alkoxy, C Calkylmercapto, trifluoromethyl, acetylamino, phenyl, phenoxy orphenylamino groups, as well as a naphthylamine radical.

Suitable acylamino groups X are those of the formula Nl-l Q "l" in whichrepresents a CO or SO bridge and T denotes a C,C -alkyl radical which isoptionally substituted, for example by chlorine, nitrile, hydroxyl or C-C -alkoxy, a cyclohexyl radical or a phenyl radical which is optionallysubstituted by halogen, such as chlorine and bromine, C -C alkyl, C -C-alkoxy or C C -alkylmercapto.

Suitable alkylmercapto groups X are preferably those with C C carbonatoms.

Suitable arylmercapto groups X are preferably phenylmercapto groupswhich can be substituted by halogen atoms, C C -alkyl or C C -alkoxyradicals.

Possible alkyl radicals R are: unsubstituted lower alkyl radicals withl-4 C atoms as well as methyl radicals substituted by hydroxyl, nitrile,C C -alkoxy, C C -alkylmercapto, C C -alkylamino, C -C dialkylamino(possibly part of a ring), cyclohexylamino, aryloxy or arylmercaptogroups, with aryl to be understood preferentially as phenyl, ornaphthyl, optionally substituted by C C -alkyl, C C;- alkylmercapto, C C-alkoxy and halogen.

As examples there may be mentioned: methyl, ethyl, propyl, butyl,ethoxymethyl, propoxymethyl, butoxymethyl, hexoxymethyl,cyclohexoxymethyl, ethylmercaptomethyl, butylmercaptomethyl,octylmercaptomethyl, phenoxymethyl, 4-chlorophenoxymethyl, 3-methylphenoxymethyl, 2,4-dimethylphenoxymethyl,

OCH -GCH I 2 g 2 i I Pl c -O in which R has the abovementioned meaningas well as those of the formula i o 2 00H -C-CH I a v 0 IH-P in which Rhas the abovementioned meaning and P represents a cyclohexyl radicalwhich is optionally substituted by C C -alkyl or a phenyl radical whichis optionally substituted by halogen, C -C alkyl or C C -alkoxy. The newanthraquinone compounds of the formula I are obtained by reactinganthraquinone derivatives of the formula in which X X and Y have theabovementioned meaning and E represents a replaceable substituent,

with 3-hydroxymethyl-oxetanes of the formula BIO-CH2 t c, V l I l s t-chydroxymethyloxetane,

hydromethyloxetane, 3,3-bis-hydroxymethyloxetane,

in which R has the indicated meaning in the presence of stronglyalkaline compounds, if appropriate in the presence of a suitablesolvent, at temperatures of lO-l60C, preferably l20l40C.

The reaction is preferably carried out in an excess of (V), whichsimultaneously serves as the solvent. Further suitable solvents are, forexample, dimethylformamide, dimethylacetamide, dimethylsulphoxide, N-methylpyrrolidone, e-caprolactam or pyridine.

Suitable strongly alkaline compounds are, for example, sodium hydroxideor potassium hydroxide or sodium carbonate or potassium carbonate. IPossible replaceable substituents E are in particular; halogen such aschlorine and bromine, lower alkoxy groups, optionally substitutedaryloxy groups, preferably phenoxy groups, or sulphonic acid groups.

Suitable anthraquinone compounds of the formula IV are, for example:l-amino-4-hydroxy-2-phenoxyanthraquinone,l-amino-4-hydroxy-2-(chlorophenoxy)-anthraquinone;-"l-amino-4-hydroxy-2-methoxyanthraquinone, l-amino-4-hydroxy-2-bromoanthraquinone, l-amino-4-hydroxy-2-chloroanthraquinone, l,4-diamino-2-phenoxyanthraquinone, l,4-dihydroxy-2-phenoxyanthraquinone, l,4-diamino-2-phenoxy-3-chloroanthraquinone,l,4-diamino-2-(o-chlorophenoxy)-3- l-amino-2-phenoxy-4-l-amino-2-phenoxy-4- ethoxyphenylamino-anthraquinone-2-sulphonic acid,l-amino-4-methylm ercaptophenylaminoanthraquinone-2-sulphonic acid,l-amino-4- trifluoromethyl-phenylamino-anthraquinone-2- sulphonic acid,l-amino-4-diphenylaminoanthraquinone-2-sulphonic acid, l-amino-4-phenoxyphenylamino-anthraquinone-Z-sulphonic acid andl-amino-4-naphthylamino-anthraquinone-Z- sulphonic acid.

The oxetanes of the formula V used as starting materials can bemanufactured according to processes which are in themselves known; forexample according to such processes as are described in Methoden derorganischen Chemie (Methods of Organic Chemistry) by Houben-Weyl, volumeVI/3, page 493 ff.

Suitable oxetanes of the formula V are, for example:3-methyl-3-hydroxymethyloxetane, 3-ethyl-3- 3-n-butyl-3-3-cyanomethyl-3-hydroxymethyloxetane, I 3- 4ethoxymethyl-3-hydroxymethyloxetane, 3-propoxymethyl-3-hydroxymethyloxetane, 3-butoxymethyl-3-hydroxymethyloxetane, 3hexoxymethyl-3-hydroxymethyloxetane, 3-butylmercaptomethyl-3-hydroxymethyloxetane, 3-phenoxymethyl-3-hydroxymethyl-oxetane, 3-chlorophenoxymethyl-3-hydroxymethyl-oxetane, 3-methylphenoxymethyl-3-hydroxymethyl-oxetane 3dimethylphenoxymethyl-3-hydroxymethyl-oxetane, 3-

trimethylphenoxymethyl-3-hydroxymethyl-oxetane,B-ethylphenoxymethyl-3-hydroxymethyloxetane,tert.butylphenoxymethyl-3-hydroxymethyl-oxetane,3-isooctylphenoxymethyl-3-hydroxymethyl-oxetane,3-methoxyphenoxymethyl-3-hydroxymethyl-oxetane,3-ethoxyphenoxymethyl-3-hydroxymethyl-oxetane, 3-isopropoxyphenoxymethyl-3-hydroxymethyl-oxetane,3-methylmercaptophenoxymethyl-3- hydroxymethyloxetane,3-naphth0xymethyl-3-hydroxymethyl-oxetane 3-phenylmercaptomethyl-3-hydroxymethyloxetane,3-methylphenylmercaptomethyl-3-hydroxymethyloxetane, 3tert.-butyl-phenylmercaptomethyl-3 hydroxymethyloxetane, 3-

chlorophenylmercaptomethyl-3- hydroxymethyloxetane, 3-butylaminomethyl-3hydroxymethyloxetane, 3-dimethylaminomethyl-3 hydroxymethyloxetane, 3-diethylaminomethyl-3 hydroxymethyloxetane, 3-pyrrolidinomethyl-3hydroxymethyloxetane, 3-piperidinomethyl-3 hydroxymethyloxetane and3-cyclohexylaminomethyl- 3-hydroxymethyloxetane.

The anthraquinone compounds of the formula 1 obtainable according to theprocess of the invention are valuable dyestuff intermediate products.They can, for example, be converted by means of hydrogen halide acids,if appropriate whilst using inert organic solvents, through splitting ofthe oxetane ring, into correspondinghalogenomethyl-hydroxypropoxy-anthraquinones which are new dyestuffs fordyeing synthetic fibres and fabrics.

If aliphatic carboxylic acids and hydrogen halide acids are usedsimultaneously, valuable anthraquinone dyestuffs for synthetic fibresand fabrics are again obtained, which in addition to the halogenomethylgroup also contain an acyloxy group in the side chain. The oxetane ringcontained in the anthraquinone compounds of the formula I is furthermoreaccessible to additional reactions such as are described, for example,in Methoden der organischen Chemie (Methods of Organic Chemistry) byHouben-Weyl, volume Vl/3, page 510 ff.

However the compounds of the formula I, optionally a mixed with oneanother, are also outstandingly suitable for dyeing and printingsynthetic fibres and fabrics", for example of cellulose triacetate,polyamides or, preferably, aromatic polyesters. They are dyed or printedin accordance with the methods customary for these fibres. Cellulosetriacetate and polyamide fibres can be dyed at about 100C, optionally inthe presence of the customary auxiliaries. When dyeing fibres ofaromatic polyesters, for example polyethylene glycol terephthalate, thecustomary carrierscan be added or the dyeing can be carried outwithout'addition of carrier, at

It is advantageous to reduce the dyestuffs to a finely divided state inaccordance with the customary methods before they are used, for exampleby grinding or kneading, preferably in the presence of customarydispersing agents.

Using the abovementioned processes, strong clear yellow, red or bluedyeings of very good fastness properties, especially excellent fastnessto light, sublimation and thermofixing, are obtained with theanthraquinone compounds of the formula I on the fibres mentioned.

A further subject of the present invention are new anthraquinonecompunds of the formula in which X, denotes a hydroxyl or amino group,

X denotes a hydroxyl, amino, alkylamino, cycloalkylamino, arylamino,acylamino, alkylmercapto or arylmercapto group,

Y represents hydrogen, halogen, alkylmercapto or arylmercapto radicals,

R represents an alkyl radical,

l-lal represents chlorine, bromine or iodine and Z represents hydrogenor an acyl radical, as well as their manufacture and use for dyeing andprinting synthetic fibre materials.

The radicals X,, X Y and R have already been defined in more detailabove.

Possible acyl radicals Z are: alkylcarbonyl, cycloalkylcarbonyl,aralkylcarbonyl and arylcarbonyl radicals.

Suitable alkylcarbonyl radicals are those with 1 to 17 C atoms in thealkyl radicals, which can be further substituted by halogen, preferablyCl, acetyl, phenoxy, nitrile and C C ,-alkoxy.

A suitable cycloalkylcarbonyl radical is the cyclohexylcarbonyl radical.

Suitable aralkylcarbonyl radicals are radicals of phenylacetic acid andcinnamic acid.

Suitable arylcarbonyl radicals are benzoyl radicals which are optionallysubstituted, for example by halogen, preferably Cl, C,-C -all yl, C,C-alkoxy, phenyl or phenoxy, as well as radicals of the naphthoic acids.

Preferred dyestuffs of the formula (1) are those of the formula in whichX X Y and R have the abovementioned meaning with hydrogen halide acids,optionally in the presence of organic solvents.

The hydrogen halide acids can be employed both in a dilute orconcentrated aqueous form and in a gaseous form, and in the former casethe organic solvents possibly to be used are advantageously misciblewith water whilst when using gaseous hydrogen halide acids it isadvisable to use inert solvents which are immiscible with water.

Suitable solvents are, in addition to aromatic hydrocarbons such asbenzene, toluene, xylene, chlorobenzene, dichlorobenzene, nitrobenzeneand anisole, alcohols such as methanol, ethanol, propanol and butanol,as well as ethylene glycol monomethyl or dimethyl or monoethyl ordiethyl ethers, tetrahydrofurane, dioxane, dimethylsulphoxide,sulpholane, N- methylpyrrolidone, dimethylformamide, caprolactam, carbontetrachloride, acetone, methyl ethyl ketone, cyclohexanone and others.

ln carrying out the process in practice, the general procedure is towarm the starting materials (4), in the appropriate aqueous hydrogenhalide acid as the reaction medium, to 80C for a brief time, or to passhydrogen halide into the solution or suspension of (4) in suitablesolvents, preferably at 30lO0C, or to add aqueous hydrogen halide acidsdropwise and subsequently to isolate the resulting reaction products byprecipitation with methanol or water or by driving off the solvent used.

Those anthraquinone dyestuffs of the formula (1) in which v Z representsan acyl radical are obtained by esterification of the compounds of theformula l in which Z represents hydrogen in accordance with methodswhich are in themselves known, by reaction with suitable alkyl-,cycloalkyl-, aralkylor aryl-carboxylic acids or their functionalderivatives, by which there are to be understood the acid anhydrides andpossibly also the acid halides and acid esters.

The appropriate derivatives of the following acids may be mentioned asexamples: acetic acid, chloroacetic acid, dichloroacetic acid,trichloroacetic acid, propionic acid, butyric acid, pentanoic acid, 2-methylbutyric acid, trimethylacetic acid, isobutyric acid,2-ethylbutyric acid, hexanoic acid, heptanoic acid, octanoic acid,decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid,methoxyacetic acid, ethoxyacetic acid, acetoacetic acid, cyanoaceticacid, cyclohexanecarboxylic acid, benzoic acid, chlorobenzoic acid,methylbenzoic acid, ethylbenzoic acid, p-tert.butylbenzoic acid,methoxybenzoic acid, dichlorobenzoic acid, phenylbenzoic acid,phenoxybenzoic acid, benzophenonecarboxylic acid, phenoxyacetic acid,phenylacetic acid and naphthoic acid.

In some cases it has proved advantageous if the dyestuffs of the formula(1) in which Z denotes an acyl radical are manufactured in a one-potprocess which is characterised in that anthraquinone compounds of theformula x, n n A O-GH -c-cn 2 I I 2 n c-o I Y in which X X Y and R havethe indicated meaning are reacted with an inorganic acid halide in anexcess alkanecarboxylic acid and optionally in the presence of an inertsolvent.

m2 ocn (icn 10 above, by replacing the relatively expensive inorganicacid halides by a hydrogen halide acid.

Here, an appropriate procedure is to treat the anthraquinone compoundsof the formula (4), dissolved or suspended in excess alkanecarboxylicacid, for example acetic acid, optionally in the presence of an inertorganic solvent, with at least one equivalent of gaseous hydrogen halideat temperatures of 0 to 200C, preferably to 150C. The water liberated inthe reaction is appropriately distilled off azeotropically, using suit-0 able entraining agents such as benzene.

The anthraquinone compounds of the formula (4) required as the startingmaterial for the various processes are new. These compounds areobtained, for example, in accordance with the process indicated earlier25 by reacting anthraquinone derivatives of the formula in which X X andY have the indicated meaning and E represents a replaceable substituent,in the presence of an acid acceptor and optionally in an organicsolvent, with 3-hydroxymethyloxetanes of the formula 4 '3 HO-Cli (6) inwhich R has the abovementioned meaning.

Examples of anthraquinone derivatives of the formula 4) are:

- Continued NH f k 0 I CH C (1H H C-0 0 s 2 0 NH i ocfi -c-cn H C-OllllH f O H H or the dyeing can be carried out without addition of 2OCHQ C CH 2 093943-932 carrier at ll C, under pressure. The dyeings can2 6 also be fixed by a brief heat treatment at 190220C. NH 2 O NH 5 2 40lit is advantageous if, before use, the dyestuffs are reduced to afinely divided state in accordance with the customary methods, forexample by grinding or kneading, preferably in the presence of customarydispersing in which R can in all cases represent agents.

CH -C H CH 0H w o 9 CH I -CH SC H 9 2 4 9 CH N or on u H CH The newdyestuffs of the formula (1) are outstand- The dyestuffs according tothe invention are furtheringly suitable, optionally also mixed with oneanother, more in Pa u ta l f r the Continuous dyeing of synfor dyeingsynthetic materials, especially for dyeing th tlc fibre materials fromorganic solvents which are and/or printing fibres, filaments, wovenfabrics, knitted lmmiSCible ith Water and Of which the boiling pointslie between 40 and 150C, these being especially aliphatic chlorinatedhydrocarbons, such as tetrachlorofabrics, tapes, films or sheets ofsynthetic origin, but

above all for dyeing and printing synthetic fibre materi- 6O als. Theyare dyed or printed in accordance with the ethylene, trichloroethyleneand 1,1,1- methods customary for the fibres. Cellulose triacetatetrichloroethylene, as well as aliphatic fluoroor fluoroand polyamidefibres can be dyed at about lO0C.from chloro-hydrocarbons, such asperfluoro-n-hexane, 1,2,- aqueous liquors, optionally in the presence ofthe cus- 2-trifluoro-trichloroethane and l,l,l-trifluoropentatomaryauxiliaries. When dyeing fibres of aromatic chloropropane and aromaticchloroand fluorohydropolyesters, for example polyethylene glycolterephthalcarbons, such as chlorobenzene, fluorobenzene, chloate, thecustomary carriers can be added to the dyebath rotoluene andbenzotrifluoride.

For dyeing, the dyestuffs to be used according to the invention aredissolved in water-immiscible organic solvents or are added to these inthe form of solutions in solvents which are infinitely misciblewith-these solvents, such as alcohols, dimethylformamide,dimethylacetamide, dimethylsulphoxide or sulpholane, and the syntheticfibre materials are impregnated with the resulting clear dyestuffsolutions which can optionally additionally contain soluble non-ionicauxiliaries, for example the known surface-active oxethylation andpropoxylation products of fatty alcohols, alkylphenols, fatty acidamides and fatty acids, in' order to improve the evenness of thedyeings. Thereafter, the dyestuffs are fixed onto the fibre materials bya heat treatment. The heat treatment can consist of a brief dry heattreatment at 120-230C, with the dry heat treatment optionally beingpreceded by an intermediate drying, or can consist of a treatment of thefibre materials in superheated solvent vapour at ll50C. Smallproportions of non-fixed dyestuff can be eluted by brief treatment withthe cold organic solvent. It should be pointed out that mixtures of thedyestuffs to be used according to the invention at times give a bettercolour yield than the individual dyestuffs and may display bettersolubility in the organic medium.

Using the abovementioned process, strong orangecoloured red or violetdyeings of good fastness properties, especially good fastness to light,sublimation and thermofixing, are obtained with the dyestuffs of theformula (l) on the fibres mentioned.

In the examples which follow, unless otherwise stated, the partsindicated are parts by weight.

a. 100 parts of 3-hydroxymethyl-3-ethyloxetane are mixed with 100 partsof e-caprolactam and 4 parts of powdered potassium hydroxide. Afteradding 30 parts of l-amino-2-phenoxy-4-hydroxy-anthraquinone thereaction mixture i's stirred for 4 /2. hours at l30140C, subsequentlycooled to approx. 60C and treated with 200 parts by volume of methanol.The red dyestuff crystals which have separated out are filtered off andwashed with methanol and water. 26.5 parts of the indicated compound,melting at 2379C after recrystallisation from glacial acetic acid, areobtained.

b. If the procedure indicated in Example 1a is fol lowed, but using 300parts of 3-hydroxymethyl-3- ethyloxetane and without the addition of afurther solvent, 25.2 parts of the same compound are obtained after 12hours reaction time.

c. 1 part of this dyestuff, which has beforehand been reduced to afinely divided state in the presence of dispersing agents, is dispersedin 400 parts of water. 100 parts of polyester fibres (polyethyleneterephthalate) are dyed in the resulting dyebath, in the presence of 15parts of o-cresotic acid methyl ester as the carrier, for 120 minutes atthe boil. A clear red dyeing of very good fastness to light and tosublimation is obtained.

' EXAMPLE 2' v cn 0 1m .2 firl V on z a. 30 parts ofl-amino-2-phenoxy-4-hydroxyanthraquinone are introduced into a mixtureof parts of 3-hydroxymethyl-3-methyloxetane, 60 parts-ofN-methylpyrrolidone and 4 parts of potassium hydroxide. After heating to130-140C for 2 hours, the transetherification is complete. The mixtureis diluted with 200 parts by volume of methanol and the dyestuff whichhas separated out is filtered off and washed with methanol and water.26.7 parts of ,the indicated compound, melting at 248-50C afterrecrystallisation from pyridine, are obtained.

b. The same dyestuff is obtained if instead of lamino-2phenoxy-4-hydroxy-anthraquinone, l-amino-2-methoxy-4-hydroxy-anthraquinone is employed, or if potassium hydroxideis replaced by sodium hydroxide.

c. parts of 3-hydroxymethyl-3-methyloxetane, 10 parts of phenol, 2 partsof potassium hydroxide and 10 parts ofl-amino-2-bromo-4-hydroxy-anthraquinone are heated to C until no furtherstarting material is' detectable. After completion of the reaction, themixture is cooled to about 80C and 100 parts by volume of methanol, 20parts of water and 2 parts of glacial acetic acid are added. Thedyestuff which has separated out is filtered off after cooling, washedwith methanol and water and dried. 8.3 parts of the indicated compoundare obbtained.

d. 100 parts of polyester fibres (polyethylene terephthalate) are dyedwith 1 part of this dyestuff, which has beforehand been brought to afinely divided state with the customary auxiliaries, in 3,000 parts ofwater for 1 hour at l25l 30C under pressure. A strong, red dyeing havingvery good fastness properties is obtained.

EXAMPLE 3 OH 00H I Weave-(m on n c-o a. 120 parts of3-hydroxymethyl-3-ethyloxetane, parts of e-caprolactam, 4 parts ofpotassium hydroxide and 33 parts ofl,4-dihydroxy-Z-p-chlorophenoxyanthraquinone are heated to l30l40C for 4hours. After working-up with methanol and water, 27.3-parts of theindicated compound are obtained, melting at l68-9C afterrecrystallisation from pyridine.

b. 100 parts of polyester fibres (obtained by polycondensation ofterephthalic acid with dimethylolcyclohexane) are dyed with 1 part ofthis dyestuff, which has beforehand been brought to a finely dividedstate with customary auxiliaries, in 3,000 parts of water for one hourat l25-l30C under pressure. A strong, orange dyeing having very goodfastness properties is obtained.

EXAMPLE 4 parts of the indicated compound are obtained, melting at l756Cafter recrystallisation from pyridine.

b. A fabric of polyester fibres (polyethylene terephthalate) isimpregnated on a padder with a liquor which contains, per litre, 20 g ofdyestuff of the above structure which has beforehand been brought to afinely divided state in the presence of dispersing agents. The fabric issqueezed out to a weight increase of 70% and is dried at 100C.Thereafter it is treated with hot air for 60 seconds at 190220C in orderto fix the dyeing, rinsed, washed hot and dried. A strong red dyeing ofvery good fastness to light, sublimation and rubbing is obtained.

EXAMPLE parts 1-amino-4--hexahydroanilino- 0 hand been brought to afinely divided state in accordance with the customary methods, in 4,000parts of water for 1 hour at 100C. The fabric is subsequently rinsedwarm and cold, and dried. A clear violet dyeing of very good fastness towashing and to light is obtained.

EXAMPLES 6-30 The anthraquinone compounds (A) listed in Table 1,'

which are characterised by their melting points given in 0 the table,are manufactured analogously to the description in Examples 1-5.

. ,OCH 41-011 anthraqu1none-2-sulphor11c acid are mlxed wlth 40 i i 2parts of 3-hydroxymethyl-3-ethyloxetane and 20 parts Y H ofN-methylpyrrolidone. After adding 2 parts of potas- 2 Table 1 Example XX, Y R Melting point [C] 6 NH, NH, H cm, 167 s 7 0H OH H CH, 210 1 8 NH,NH H c,H, 238

9 NH, s Q0 H cm, 248 9 10 NH, NH, Cl c,H,, 168 9 11 NH, NH -co-c11 H c,H6

12 NH NH H CH, 167-8 13 NH, NH-@c1 H c,H 227-8 14 NH, NH H c. H, 169 7015 NH. NH H c,H, 182 3 l6 NH NH @011 H c,H 198 200 17 NH, 5 @cmw H c,H,274-5 18 NH, s H c,H,, 207 9 19 NH, 5 Q H c,H, 181-2 20 NH, 5 H C,H,-,233 4 21 NH: SC4H, H (32H; 142 3 22 NH, NH. 5 --c1 c,H 132 s 23 NH, NH,s c,H 1

Melting point P Example x, x Y R 24 NH, NHCO--(CH CH H C 11 1.0 844 2sNH NH-CO-O H C2H5 5 26 NH NH co-@ H -C H 229-30 27 NH Nil-SO20 H C H.-,201 3 28 OH H CH O-Q-U 227-8 29 NH OH H (m c-411 175-6 30 NHZ OH H CH Om186-7 EXAMPLE 3 a. 20 parts of 3-phenoxymethyl-3- CH CHhydroxymethyloxetane, 20 parts of e-caprolactam, 1 2 part of powderedpotassium hydroxide and 5 parts of (In o-03l-amino-2-phenoxy-4-hydroxy-anthraquinone are I heated to l30140C for 5%hours. After cooling to g approx. 80C, 50 parts by volume of methanolare a. 45 parts of 3,3-bis-hydroxymethyl-oxetane, parts ofN-methylpyrrolidone, 2 parts of potassium hydroxide and 8 parts of1-amino-2-phenoxy-4-hydroxyanthraquinone are heated to -l130C for 1%hours. After cooling, the resulting dyestuff is separated out by meansof 60 parts by volume of methanol, filtered off and washed with methanoland water. 7.7 parts of the indicated compound are obtained, melting at239240C after recrystallisation from anisole.

b. 100 parts of a fabric of texturised polyethyleneterephthalate fibresare introduced at room temperature, without prior cleaning, into adyebath which contains 1 part of the dyestuff manufactured according toExample 31a in 1,000 parts of tetrachloroethylene. The bath is heated to115C over the course of 10 minutes with vigorous circulation of theliquor and is kept at this temperature for minutes. Then the liquor isseparated off and the dyed goods are rinsed for 5 minutes with freshsolvent at approx. 40C. After separating off the rinsing liquor, thedyed goods are centrifuged and dried in a stream of air. A red dyeing ofvery good fastness to sublimation and very good fastness to washing andlight is obtained.

An equivalent red dyeing was obtained in the same manner on a fabric ofpolycyclohexane-dimethylene- I ocH -C-CH added. The dyestuff which hasseparated out is filtered off after cooling and is washed with methanoland water. 5.8 parts of the indicated compound, melting at 162-3C afterrecrystallisation from pyridine, are obtained.

b. A previously cleaned and thermofixed fabric of polyethyleneterephthalate is printed with a paste consisting of the followingconstituents:

20 g of dyestuff, obtained according to Example 32a,

in a finely divided form 520 g of water 450 g of crystal gum, 1:2

10 g of cresotic acid methyl ester. In order to fix the dyestuff, theprinted and dried goods are treated with hot air for 40 seconds at 200C.After soaping, rinsing and drying, a clear red print of very goodfastness to light and to sublimation is obtained.

EXAMPLES 33-60 ,l E o c a -ci-c 2 (B) Y 11 0-0 Table 2Continued ColourExample X X Y R shade 73 NH2 OH CH; 44:] Red 74 NH H CH2-NH-C3H1 Red 75Nl-l OH H CH2-NHO Red EXAMPLE 76 EXAMPLE 79 ca -s- CH 0 m2 0 on c: :1! 0m2 2 2 o-cn -c-cn W g, @0 H 0 on 2 l E a c-o 30 parts of3-hydroxymethyl-3-phenylmercap- 26 parts of 3 hydroxymethyl 3tomethyl-oxetane (manufactured from the corresponding bromomethylcompound and thiophenol), 20 parts of e-caprolactam, 1.5 parts ofpowdered potassium hydroxide and 7.5 parts of l-amino-2-phenoxy-4-hydroxy-anthraquinone are heated to l30l40C for 2% hours. After adding60 parts by volume of methano], the dyestuff which has separated out isfiltered off, washed with methanol and water and dried. 8.7 parts of theabove compound are obtained, melting at 194-5C after recrystallisationfrom pyridine.

EXAMPLE 77 CH-O-CH ONE 2 10 parts of3-hydroxymethyl-3-ethoxymethyloxetane (manufactured from the3-bromomethyl compound and sodium ethylate), 6 parts of N-methylpyrrolidone, 0.5 part of powdered potassium hydroxide and 2.5parts of l-amino-2-(p-chlorophenoxy 4-hydroxy-anthraquinone are heatedto l-l40C for 4% hours. After adding 25 parts by volume of methanol, thedyestuff which has separated out is filteredoff, washed with methanoland water and dried. 2.4 parts of the indicated compound,- melting at149-50C after recrystallisation from pyridine, are obtained.

EXAMPLE 78 3-cyanomethyl-3-hydroxymethyl-oxetane Ypiperidinomethyloxetane (manufactured from the 3-- EXAMPLE 80 ,ca cu -n3 0 c: "\CH o-cn -c-cn t on a c-o If, in the preceding example,3'-hydroxymethyl-3- piperidinomethyl-oxetane is replaced by the sameamount of analogously manufactured 3-hydroxymethyl-3-dimethyl-aminomethyl-oxetane, 3.2 parts of a dyestuff ofthe indicated formula, melting at llC after recrystallisation frompyridine, are obtained.

EXAMPLE I a. 5 parts of 3-(l-amino-4-hydroxy-anthraquinonyl-2)-oxymethyl-3-ethyl-oxetane are introduced into parts of concentratedaqueous hydrochloric acid and t the mixture is stirred for one-half hourat room temperature. The reaction mixture is subsequently poured into500 parts of water and the product is filtered off, washed with wateruntil neutral and dried. 5.5 parts of the indicated compound, melting atl68-9C after recrystallisation from pyridine, are obtained.

b. 1 part of this dyestuff, which has beforehand been brought to afinely divided state in the presence of dispersingj agents, is dispersedin 4,000 parts of water.

parts of polyester fibres (polyethylene tere'phthalate) are dyed in theresulting dyebath, in the presence of 15 parts of o-cresotic acid methylester as the carrier, for 120 minutes at the boil. A strong, clear, reddyeing of very good fastness properties, especially excellent fastnessto light and sublimation, is obtained.

a. 3 .5 parts of 3-(l-amino-4-hydroxyanthraquinonyl-Z)-oxymethyl-3-methyl-oxetane in 40parts of methyl ethyl ketone are heated to the boil with 3 parts ofaqueous concentrated hydrochloric acid for minutes. thereafter, 30 partsby volume of methanol and 40 parts of water are added and the product isfiltered off cold. After washing with water and drying, 3.6 parts of theindicated compound, melting at 2101 1C after recystallisation fromchlorobenzene, are obtained.

b. lf, in Example 11a, methyl ethyl ltetone is replaced by the sameamount of tetrahydrofurane, dioxane, ethylene glycol dimethyl ether,dimethylformamide or N- methylpyrrolidone and in other respects theindicated procedure is followed, the same dyestuff is obtained.

c. 100 parts of polyester fibres (polyethylene terephthalate) are dyedwith 1 part of this dyestuff, which has beforehand been brought to afinely divided state with the customary auxiliaries, in 3,000 parts ofwater for 1 hour at 125-130C under pressure. A clear, strong red dyeinghaving very good fastness properties is obtained.

EXAMPLE 111 a. 18 parts of 3-( l-amino-4hydroxy-anthraquinonyl-2)-oxyrnethyl-3hydroxyrnethyloxetane are suspended in 100 parts ofaqueous concentrated hydrochloric acid and the mixture is stirred forone-half hour at 40C. After dilution with 500 parts of water, theproduct is filtered off and washed with water until neutral. 18.8 partsof the indicated compound, melting at 2467C after recrystallisation fromanisole, are obtained.

b. 100 parts of a fabric of texturised polyethylene terephthalate fibresare introduced, without prior cleaning, into a dyebath at roomtemperature which has been prepared from 1 part of the dyestuffmanufactured according to 111 and 1,000 parts of tetrachloroethylene.The bath is heated to 115C over the course of minutes with vigorouscirculation of the liquor and is kept at this temperature for 30minutes. The liquor is then separated off and the dyed goods are rinsedwith fresh solvent at approx. 40C for 5 minutes. After separating offthe rinsing liquor, the dyed goods are centrifuged and dried in a streamof air. A strong red dyeing of excellent fastness to sublimation andvery good fastness to washing and tolight is obtained.

An equivalent red dyeing was obtained analogously on a fabric ofpolycyclohexane-dimethyleneterephthalate fibres.

1f the tetrachloroethylene is replaced by the same amount of1,1,2-trichloroethane, an equivalent dyeing is obtained.

EXAMPLE 1V 5 CH4 0 m 1 9 k OCH =C-CH 0H t l a. 4 parts of3-(l-amino-4-hydroxy-anthraquinonyl- 2-)-oxymethyl-3-methyl-oxetane in40 parts of tetrahydrofurane are treated with 4 parts of 48% strengthaqueous hydrobromic acid and the mixture is warmed to 50-60C for 5minutes. After adding 50 parts by volume of methanol and 100 parts ofwater, and working-up as usual, 4.7 parts of dyestuff, melting at 2023Cafter recrystallisation from chlorobenzene, are obtained.

b. A dyebath is prepared from 1 part of the above dyestuff which hasbeforehand been brought to a finely divided state using the auxiliariescustomary for the purpose, 6 parts of fatty alcohol-sulphonate and 3,000parts of water, and 100 parts of cellulose triacetate fibres are dyedtherein for 1 hour at 100C. A yellowish-tinged red dyeing of very goodfastness to washing, thermofixing and light is obtained.

EXAMPLE V EXAMPLE V1 on NH 1 OCH2-==C==CH2OH y l l a. 5 parts of3-(1-amino-4-cyclohexylaminoanthraquinonyl-2)-oxymethyl-3-ethyloxetanein parts of acetone are heated to the boil with 6 parts of 48% strengthhydrobromic acid for 2 minutes. After adding 30 parts by volume ofmethanol and 40 parts of water, and dyestuff which has separated out isfiltered off and washed with water. 5.1 parts of the indicated compound,melting at 1534C after recrystallisation from benzene, are obtained.

b. 100 parts of polyamide fabric are dyed with 1 part of the dyestuffmanufactured in this way, which has beforehand been brought to a finelydivided state in accordance with the customary methods, in 4,000 partsof water for 1 hour at 100C. The fabric is subsequently rinsed warm andcold and dried. A strong violet dyeing of very good fastness to washingand light is obtained.

EXAMPLE v11 a. parts of 3-(1amino-4-hydroxy-anthraquinonyl-2)-oxymethyl-3ethyloxetane in 60 parts of methyl ethyl ketone are heatedto the boil. After stopping the heating, hydrogen chloride gas is passedin for 5 minutes, whereupon a clear red dyestuff solution is obtainedafter a short time. The solution is diluted with 30 parts by volume ofmethanol and 60 parts of water and after working-up 5.3 parts of adyestuff identical with that manufactured in Example la are obtained.

b. If, in Example VIla, methyl ethyl ketone is replaced by the sameamount of benzene, tetramethylenesulphone, anisole, carbon tetrachlorideor butanol and in other respects the procedure indicated is followed,the reaction product separates out as the yellow hydrochloride, which isfiltered off, washed with the particular solvent and converted into thedyestuff of Example Ia by treatment with methanol and water.

c. 100 parts of 3hydroxymethyl-3-ethyloxetane, 100 parts ofe-caprolactam, 4 parts of potassium hydroxide and 30 parts of1amino2-phenoxy-4-hydroxyanthraquinone are heated to l30l40C for 4 /2hours. Thereafter the mixture is cooled to 80C and hydrogen chloride gasis passed in at this temperature, for minutes. 200 parts by volume ofmethanol and 220 parts of water are then added. The dyestuff which hasseparated out is filtered off and washed with water. 27.8 parts ofproduct which is identical with that manufactured according to ExampleIa and dyes polyester materials in red shades having very good fastnessproperties are obtained.

EXAMPLE VIII C H m I 5 OCH -(I-CH 0H o ZCI CH -Cl a. 3.5 parts of 3-(1,4-diamino-3-chloroanthraquinonyl-2 )-oxymethyl-3ethyloxetane togetherwith 50 parts of ethylene glycol monoethyl ether and 4 parts of aqueousconcentrated hydrochloric acid are warmed to 6070C for 5 minutes. Theresulting dyestuff is separated out by adding 50 parts by volume ofmethanol and parts of water, filtered off and washed with water. 3.7parts of the indicated compound, melting at 1978C afterrecrystallisation from pyridine, are obtained.

b. 100 parts of polyester fibres (polyethylene terephthalate) are dyedwith 1 part of this dyestuff, which has beforehand been brought to afinely divided state EXAMPLE IX cn o OH I25 10 parts of 3-(l,4-dihydroxy-anthraquinonyl-2)- oxyrnethyl-3-ethyloxetane are dissolvedin 100 parts of dime thylsulphoxide at-80C. After adding 8 parts ofaqueous concentrated hydrochloric acid, the mixture is EXAMPLE X CH -C1a. 4.5 parts of 3-( l,4-diamino-anthraquinonyl-2)-oxymethyl-3-ethyloxetane are dissovled in 45 parts ofN-methylpyrrolidone. After adding 3.8 parts of lauric acid chloride at30-40C, the mixture is stirred for a further one-half hour at 30C. Thereaction product is separated out by adding SO'parts by volume ofmethanol and 20 parts of water, whilst cooling with ice, and is filteredoff and washed with 50% strength aqueous methanol. 6.6 parts of theindicated compound, melting at 6l2C after recrystallisation frompyridine, are obtained.

b. A polyethylene terephthalate fibre fabric is impregnated at roomtemperature with a clear red solution which contains 10 parts of thedyestuff according to Example Xa and '7 parts of nonylphenolheptaethylene-glycol ether in 983 parts of tetrachloroethylene. Aftersqueezing-out to a weight increase of 60%, the fabric is dried for oneminute at C. Thereafter the dyestuff is fixed by heating the fabric to-220C for 45 seconds. The small proportion of non-fixed dyestuff is theneluted by brief rinsing with cold tetrachloroethylene. After drying, aclear bluish-tinged red dyeing is obtained, which is distinguished byits very good build-up and by its good fastness properties.

EXAMPLE XI 5 parts of 3-(lamino-4-hydroxy-anthraquinonyl-2)-oxymethyl-B-ethyloxetane in 50 parts of methyl ethyl ketone are warmedto 50C. The reaction mixture is treated with 3 parts of aqueousconcentrated hydrochloric acid and 1 part of 48% strength hydrobromicacid and is heated to the boil for 5 minutes. After adding 30 parts byvolume of methanol and 70 parts of water, the reaction product which hasseparated out is filtered off and washed with water. 5.5 parts of adyestuff mixture of which the components are identical with thedyestuffs described in Example I and XII are obtained.

On polyester fibres, the indicated dyestuff mixture yields'a strong reddyeing of very good fastness properties.

EXAMPLE XII XLIV If an analogous procedure to that'indicated in ExamplesI-X is followed with appropriate anthraquinonyloxymethyl-oxetanes, thedyestuffs listed in Table I are obtained, which have the meltingpointsindicated in the table and yield the indicated shadeon woven orknitted fabrics of polyester, triacetate, polyamide,

polyurethane or polyolefinefibres.

EXAMPLE XLV a. 25 parts of3-(l-amino-4-p-tosylaminoanthraquinonyl-2)-oxymethyl-3-ethyl-oxetane in300 parts of methyl ethyl ketone are heated with 30 parts of aqueousconcentratedhydrochloric acid to the boil for 5 minutes. After adding200 parts by volume of methanol and 200 parts of water, the dyestuffwhich has separated out is filtered off, washed with water and dried.24.7 parts of the indicated compound, melting at l84-5C afterrecrystallisation from pyridine, are obtained.

b. A fabric of polyester fibres (polyethylene terephthalate) isimpregnated on a padder with a liquor which per litre contains g ofdyestuff according to Example XLVa, which has beforehand been broughtinto a finely divided state in the presence of dispersing agentscustomary for the purpose. The fabric is squeezed-out to a weightincrease of 70% and is dried at 100C. Thereafter it is treated with hotair at 190220C for 60 seconds to fix the dyeing, rinsed, washed hot anddried. A strong red dyeing of very good fastness to light, sublimationand rubbing is obtained.

EXAMPLE XLVI I CH -Cl and parts by volume of ethanol and 15 parts ofwater are added, 5.3 parts of a dyestuff identical with thatmanufactured according to Example XLVIa or b are obtained.

a. 4.2 parts of 3-(l-amino-4-m-tolylmercaptoanthraquinonyl-2)-oxymethyl3-ethyl-oxetane in 60 parts of glacial acetic acid and 20 parts ofbenzene are After adding 60 parts by volume 'of ethanol and 20 parts ofice, the dyestuff which has separated out is filtered off and washedwith strength aqueous methanol. 4.6 parts'of the indicated compound,melting at l378C after recrystallisation from pyridine, are obtained.

b. A polyethylene terephthalate fibre fabric is impregnated at roomtemperature with a clear red solution which contains 10 parts of thedyestuff manufac tured according to Example. XLVlIa in 990 parts oftetrachloroethylene. After squeezing-out to a weight increaseof thefabric is dried for 1 minute at C.

a. 5 parts of 3-(l-amino-4-hydroxy-anthraquinonyl-2)-oxymethyl-3-ethyloxetane are suspended in 60 parts of glacial aceticacid and the .mixture is warmed to 80C. Hydrogen chloride gas is passedin at this temperature for 10 minutes.'60 parts of benzene are added tothe reaction batch and hydrogen chloridegas is passed in for lhour, inthe course of which benzene, glacial acetic acid and water aredistilledoff simultaneously. After adding 60 parts by. volume ofmethanol, the dyestuff which has separated out is filtered off andwashed with methanol and water. 5.5 parts of the indicated compound,melting at l8l-3C after recrystallisation from pyridine, are obtained. 7

On polyethylene terephthalate fibres, this dyestuff yields a clear,yellowish-tinged red. dyeing of very good fastness properties if theinstructions of Example II c are followed.

b. Thesame dyestuff as described in Example XLVIa is obtained if 5 partsof the starting material described there, in 60 parts of glacial aceticacid, are treated with 6.4 parts of thionyl chloride and the mixture isstirred for 15 minutes at 35C. I

c. If 5.3 parts of l amino-4-hydroxy-2-(2-ethyl-2-chloromethyl-3-hydroxypropoxy)-anthraquinone, manufactured according toExample la, in 30 parts of glacial acetic'acid are heated for 5 hours tothe boil in the presence of 0.7 parts of anhydrous sodium acetate,

Thereafter the dyestuff is fixed by heating the fabric to l-220C for 45seconds. Thereafter the small proportion of non-fixed dyestuff is elutedby a brief treatment for 20 seconds in cold tetrachloroethylene. Afterdrying, a clear, bluish-tinged red dyeing is obtained which isdistinguished by its high dyestuff yield, very good build-up and verygood fastness properties, especially very good fastness to thermofixing,washing, rubbing and light.

Equivalent bluish-tinged red analogously also on fabrics of a. cellulosetriacetate b. synthetic polyamides or polyurethanes and c. polypropylenefibres except that the thermosol treatment was carried out at 200220Cfor (a) at 170-200C for (b) and at -l50C for (0).

Equivalent dyeings were also obtained if the 990 parts oftetrachloroethylene were replaced by the same amount of one of thefollowing solvents: methylene chloride, chloroform, carbontetrachloride, dichloroethane, trichloroethane, trichloroethylene,tetrachloroethane, dichloropropane, l,l,l-trichloropropane,pentachloropropane, chlorobutane, dichlorobutane,. di-

dyeings were obtained chloroethane and 1 l ,1-trifluoro-pentachloropropane.

EXAMPLE XLVllI a. 8 parts of3-(1-amino-4-hexahydroanilinoanthraquinonyl-2)-oxymethyl-3-ethyl-oxetanein 80 parts of propionic acid are warmed to 80C. Hydrogen chloride gasis passed in at this temperature, whereupon the oxetane ring is firstlyopened, with addition of hydrogen chloride. After approx. 50% of thereaction product have been converted into the corresponding propionicacid ester, which is the case after approx. one-half hours introductionof hydrogen chloride, 80 parts by volume of ethanol and 20 parts of iceare added and the reaction mixture which has separated out is filteredoff. After washing and drying, 8.2 parts of a dyestuff which consists ofapproximately equal parts of the anthraquinonyl-y-hydroxypropoxycompound and its propionate are obtained.

b. 100 parts of polyamide fabric are dyed with 1 part of the dyestuffmixture manufactured in this way, which has beforehand been brought to afinely divided state in accordance with the customary methods, in 4,000parts of Water for 1 hour at 100C. The fabric is subsequently rinsedwarm and cold and dried. A strong, clear violet dyeing of very goodfastness to washing and light is obtained.

EXAMPLE XLIX to LXlV n l (MR swin 0Z Y CH Ea].

EXAMPLE laxv a. 1 part of 3-(l-amin0-4-hydroxy-anthraquinonyl-2)-oxymethyl-3-phenoxymethyloxetane in 10 parts of methyl-ethyl ketoneis heated to the boil for 5 minutes with 1 part of aqueous concentratedhydrochloric acid. The resulting dyestuff is separated out by adding 15parts by volume of methanol and 15 parts of water. After filtering off,and washing with strength aqueous methanol, 1 part of the indicatedcompound, melting at l34-5C after recrystallisation from methyl ethylketone, is obtained.

b. A previously cleaned and thermofixed fabric of polyethyleneterephthalate is printed with a paste consisting of the followingconstituents:

20 g of dyestuff obtained according to Example LXVa, in a finely dividedstate 520 g of water 450 g of crystal gum, 1:2

10 g of cresotic acid methyl ester.

To fix the dyestuff, the printed and dried goods are treated with hotair for 40 seconds at 200C. After soaping, rinsing and drying, a clearred print of very good fastness to light and sublimation is obtained.

EXAMPLES LXVI to CIV The dyestuffs listed in Table Ill are manufacturedanalogously to the description in Examples I to LXV. They yield theindicated shade on woven or knitted fabrics of polyester, triacetate,polyamide, polyurethane or polyolefine fibres.

Table 1111 Melting Exam- X, X: Y R Hal Z point Solvent Shade ple [C]xLlx Nl-l OH H c li Cl COClH ClH 151-2 Pyridine Red L Ni l on H C H Clcoccl 69-71 N Methylpyrrolidone Red Ll Nl-l on H C Hl Br COCHK 174-5N-Methylpyrrolidone Red L11 Ni l on H c li, Cl COCHCl 165-6 P ridine Redull Nll NIH-0 H C rl, C] COC ll-l -1 Glacial acetic acid Violet LIV Nlrlon n 0 H, Br coon, 154-5 N-Methylpyrrolidone Red LV Nl-l OH H C2145 ICOCK-l -6 Glacial acetic acid Red LVl Nll OH H CZHS Cl coc i l 18-20 Pridine Red LVlI NN on H c lr Cl cot:l-l crll cll-l,, 147-8 Pyridine RedLVlll Nli on H C214,, Cl co@ 17980 Pyridine Red LIX Nlicocl'l, OH H CZH,Cl cocl-l, 1 18-9 N Methylpyrrolidone Yellow LX Nil Nlrlco 1H c,l-l C1COCHJ -6 Glacial acetic acid Red LXI NlPl Nllso 0 H 0 H, Cl cocli 163-4Glacial acetic acid Red LXII NH: on H on, C1 cocH, 151-2 Pyridine RedLX111 NH. OH H CH3 Cl coc n 141-2 P ridine Red LXlV NH? OH H CHZO QC! C1COdCl-ll 141-2 Perchloroethylene Red Table llll Continued Example X1 X2Y R Hal Z Shade IC NH NHSO2Q-OCH3 H CH Br COCHK Red C NlHl- NHCOCH3 H Cll-l I COCH; Red Cl Nil-i NHCOCQHF, H C2H5 Cl COCZH5 Red on NH NHcocH HCH c1 co.cH Red cm NH moo-QC) H (:H (:1 Red crv NH. NHco G H CH C1 C0 QRed CV NH OH H CH2S-C4H Cl H Red CV1 NH OH H CH SC H Cl H Red cvn NH OHH CH2S Cl co c H Red cvm NH OH H CH S-- H (:1 H Red crx NH oH H cH -sQua-1 Br H Red cx NH OH H CH S @41 C] H Red on HH OH H cH -s --c1 c1 co-Red CXII NH OH H CH -OC H (11) Cl H Red CXlIl NH OH H CH OC H (n) C] HRed CXIV NH OH H cH -oc H m) Cl H Red CXV OH OH H CH2OC2H5 Cl COCl-lOrange cxvr NH. NH-O H CH OC H c1 H Violet cxvn NH OH H C H (n) C] H Redcxvm NIH- OH H CH2NH-C3H7 Cl H Red cxrx NH OH H CH -NH O C! H Red CXX NHOH H CH N I Cl H Red CXXl NH OH H CH 0 Cl H Red CXXll NH OH H CH -N(C HCl H Red EXAMPLE CXXlll 1 part of3-(1-amino-4-hydroxy-anthraquinonyl-2)- oxymethyl-3-ethoxymethyl-oxetanein parts of con- CH centrated aqueous hydrochloric acid is stirred for 10 m 2 2 hour at 3040C. Thereafter the reaction mixture is O-CH -C-CH -OHpoured onto ice, the precipitate obtained is filtered off, and afterwashing with water and drying 1 part of the 0 OH indicated compound isobtained, which melts at 1567C after recrystallisation from pyridine andyields a strong red dyeing of very good fastness properties on 10 partsof 3-(1-amino-4-hydroxy-anthraquinonylpolyester fibres.

2)-oxymethyl-3-phenylmercaptomethyl-oxetane in 80 parts of diethylketone are heated for 2 minutes to the EXAMPLE CXXV boil with 6 parts ofaqueous concentrated hydrochloric acid. The reaction product isseparated out by adding CH parts by volume of methanol and 30 parts ofwater, filtered off and washed with 50% strength aqueous 0-CH C-CH OHmethanol. 2.8 parts of the indicated dyestuff, melting at l502C afterrecrystallisation from perchloroeth- 2 ylene, are obtained. 1 60 Onpolyethylene terephthalate fibres, this dyestuff yields a clear reddyeing of very good fastness proper- 1 P of y y' q tiesoxymethyl-3-cyanomethyl-oxetane in 30 parts of methyl ethyl ketone isheated for 2 minutes to the boil EXAMPLE CXXIV with 1.5 parts ofconcentrated hydrochloric acid. The GE H reaction product is separatedout by adding 20 parts by 0 N32 2 2 5 volume of methanol and 20 parts ofwater. It is filtered 0-CH -C-CH -OH off and washed with water, and 1part of a dyestuff (LE Cl melting at l99200C after recrystallizationfrom 0 0H 2 chlorobenzene is obtained.

EXAMPLE CXXVI 2 w ocn -tla ca -oa ca -c1 EXAMPLE CXXVll 3 ca -n-ca 2 2 3w o-ca -ci-ca -on If an analogous procedure to that indicated in ExampleCXXVl is followed with 1 part of 3-(l-amino-4-hydroxyanthraquinonyl-Z)-oxymethyl-3-N,N-

dimethylaminomethyloxetane, 1 part of the indicated compound isobtained, which is isolated as the hydrochloride and melts at 2524Cafter recrystallisation from dimethylsulphoxide.

We claim: 1 Anthraquinone compound of the formula X l l OCH2-C-'-CH2-O-Z CH Hal where t T is C, C,, -alkyl, cyclohexyl,phenyl,halophenyl, C, -C, -alkylphenyl, C, C, -alkoxyphenyl, C, C,-alkylmercaptophenyl, or C, -C,, -alkyl substituted by chloro, cyano,hydroxyl or C, C., -alkoXy; Y is hydrogen,'chloro, bromo,

-sc n -sca,

-S or C H a '2 5 OCH CCH OH CH Cl 2 R is C, C, -alkyl or methylsubstituted by hydroxy, cyano, C, -C,, -alkoxy, -C, -C,, -alkylmercapto,C, -C,,- -alkylamino, phenoxy, naphthoxy, phenylmercapto,naphthylmercapto, or any of the last four radicals further substitutedby C, -C,, -alkyl, C, C, -alkylmercapto, C, -C,, -alkoxy, or halo; Halis chloro, bromo, or iodo; and

t Z is hydrogen, C, C,, -alkylcarbonyl, cyclohexylcarbonyl,phenylacetyl, cinnamoyl, benzoyl, halobenz oyl, C, -C,, -alkylbenzyl, C,-C, -alkoxybenzoyl, phenylbenzoyl, phenoxybenzoyl, naphthoyl, C, -C,-,-alkylcarbonyl substituted by halo, acetyl, phenoxy, cyano, or C, C,-alkoxy.

2. Anthraquinone compound of the formula 0CH -'f-CH -0-Z CH -Hal whereinR is methyl, ethyl, butyl, or methyl substituted by hydroxy, cyano,phenoxy, naphthoxy, chlorophenoxy, methylphenoxy, methoxyphenoxy,ethoxy, propoxy, butoxy, hexoxy, butylmercapto,

dodecylmercapto, phenylmercapto, methylphenylmercapto,t-butylphenylmercapto, chlorophenylmercapto, dimethylamino,diethylamino,

propylamino, cyclohexylamino, piperidino, morpholino, or py'rrolidino;

, is hydroxyl, cyclohexylamino, C,-C,,-

alkylcyclohexylamino, phenylamino, halophenylamino,C,'C,-alkylphenylamino, or C,C,,-

alkoxyphenylamino;

Hal is chloro, bromo, or iodo; and a Z is hydrogen or the acyl' radicalresulting fromthe removal of the hydroxyl from the carboxyl group of anacid from the group consisting of acetic acid, chloroacetic acid,dichloroacetic acid, trichloroacetic acid, propionic acid, butyric acid,pentanoic acid, 2-methylbu'tyric acid, trimethylacetic acid, isobutyricacid, Z-ethylbutyric acid, hexanoic acid, heptanoic acid, octanoic acid,decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid,methoxyacetic acid, ethoxyacetic acid, acetoacetic acid, cyanoaceticacid, cyclohexanecarboxylic acid, benzoic acid, chlorobenzoic acid,methylbenzoic 7 acid, eth'ylbenzoic acid, ptert.butylbenzoic acid,methoxylbenzoic acid, dichlorobenzoic acid, phenylbenzoic acid,phenoxybenzoic acid, benzophenonecarboxylic acid, phenoxyacetic acid,phenylacetic acid and naphthoic acid.

3. Anthraquinone compound of the formula 4. Anthraquinone compound ofthe formula C H fans 0CH -C-CH OH m ca =3: I m m 2 an -c1 O

1. ANTHRAQUINONE COMPOUND OF THE FORMULA1-X1,2-(Z-O-CH2-C(-R)(-CH2-HAL)-CH2-O-),3-Y,4-X2WHEREIN X1 IS HYDROXYLOR AMINO, X2 IS HYDROXYL, AMINO C1-C6 -ALKYLAMINO, CYCLOHEXYLAMINO,C1-C6 -ALKYLCYCLOHEXYLAMINO, PHENYLAMINO, HALOPHENYLAMINO, C1-C8-ALKYLPHENYLAMINO, C1-C4 -ALKOXYPHENYLAMINO, C1-C4-ALKYLMERCAPTOPHENYLAMINO, TRIFLUOROMETHYLPHENYLAMINO,ACETYLAMINOPHENYLAMINO, DIPHENYLAMINO, PHENOXYPHENYLAMINO,PHENYLAMINOPHENYLAMINO, NAPHTHYLAMINO, C1-C12 -ALKYLMERCAPTO,PHENYLMERCAPTO, HALOPHENYLMERCAPTO, C1-C4 -ALKYLPHENYLMERCAPTO, C1-C4-ALKOXYPHENYLMERCAPTO, OR RADICALS HAVING THE FORMULA
 2. Anthraquinonecompound of the formula
 3. Anthraquinone compound of the formula 4.Anthraquinone compound of the formula